09/03/2014 (H. Miyasaka) 2014/09/ C-H (4.3 ev) 290 nm ns 10ns 100fs ps 10

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1 /9/ C-H (. ev) 9 nm nsns s psps s s Intenal convesion Intesystem cossing i isc

2 Dono Accepte A - D 6 (Onsage) Point-dipole μ Mataga-Lippet equation e μ h a ) const. a g ( S n S n a - Stoes-Shit g : e : s : n : a : Bull. Chem. Soc. Jpn., 8, (9), Bull. Chem. Soc. Jpn., 9, 6-7 (96) α h ( a - ) / cm ( s -)/( s +)-(n -)/(n +) 7 ( E = h= hc/ h : Planc: J s : c : : m / s : nm =.6 J/mol =7.9 cal/mol=. ev= cm - cal =.8 J, ev =.6 x -9 J = 866 cm - 8

3 Enegy / (J / mol) E = h= hc/ cal =.8 J, ev =.6 x -9 J = 866 cm - Wavelength / nm Enegy / cm - 6 Wavelength / nm / (cal / mol ) / nm H-H 76 O=O 9 NN 6 7 C=O 6 Cl-Cl 8 96 I-I C-H 99 9 C-C 8 6 C=C 6 97 CC C-Cl 8 9 (IVR: intamolecula vibational Redistibution) sps psps psps 7. t t i i i i isc isc h S i S t aget Reaction

4 S S 7. h a d isc A + h A A ( d, ) A A + h (, ) A A + h (, ) da d A dt A A () exp ( ) t luoescence Intensity d ime / Abit. unit da I d A dt I A d d I I A S S h a d q isc A + h A A ( d, ) A A + h (, ) A A + h (, ) A + Q A o X ( q [Q] : Sten-Volme Plot da d q[ Q] A dt A A () exp ( Q) t luoescence Intensity d [Q] ime / Abit. unit q d d d [ Q] q d [ Q] q [ Q] [Q] / M q 6

5 Sten-Volme Plot A I A d A d dt I A A d I A I A d I [ Q] d q I d [ Q] q I / I luoescence Intensity Wavelength / nm [Q] / M 7 Sten-Volme Plot ( t= luoescence Intensity [Q] ime / Abit. unit [Q] / M t=[q] luoescence Intensity I / I [Q] ime / Abit. unit [Q] / M 8 Sten-Volme Plot Non stationay Quenching [A]/([A]+[AQ]) =/(Kg[Q]+) A +Q A + Q AQ K g I / I (AQ) [Q] / M 9 I / I Sten-Volme Plot [Q] / M A + Q (AQ)

-9-7 q 7 / (M s) d =8Rη d =8Rη 9 8. 96.9 67..6.7.9.6.6..7 6. ---- 6.. 8.. 6..7 9..6.7. ----.6 7.6 ---- 6.. Bi

6 -9-7 q 7 / (M s) d =8Rη d =8Rη Bis, J.B. : Photophysics o Aomatic Molecules (97), Wiley- Intescience, London; Belman, I.B. : Handoboo o luoescence Specta o Aomatic Molecules (97), Academic Pess, NewYo A = B d = A + B η 7. Kinetics 6

7 ps: τ ansient absoption spectoscopy τ Kinetic tansient absoption measuement 6 ansient Absoption Spectum Dieence spectum between the gound-state and the tansient state. A=log [I(w/o excitation) / I(with excitation)] I: monitoing light intensity ansient state passing though the sample Absobance Gound state (absoption spectum) 6 Wavelength Absobance.. Absobance -... Gound-state Bleaching Absoption o o the gound tansient state species Bleaching o the gound state Absoption o the tansient species ansient absoption specta -. 6 Wavelength 6 Wavelength S n S S 7 PM VDL WP ex. L WLG p. SG BS S S PD Pulsed Lase Light Souce L SG PD CPU WLG LWPVDL BSSPM SGPDSCPU h Absobance (./div.) (a) (b) (c) (d) Wavelength / nm ansient absoption specta o bianthyl obseved at ps ollowing the excitation with a nm lase pulse with ps pulse width. (a) in n-hexane, (b) in ethyl acetate, (c) in acetonitile, and (d) adsobed on the poous glass. J. Phys. Chem.,. A 6 [] ()

), DM (photodetecto o the monitoing beam), DR (photodetecto o the eeence beam), and DE (photodetecto beam o the pobe beam intensity). Chem. Phys. Lett.

8 Kinetic tansient absoption measuement Absobance ( s ) Schematic diagam o dual OPA emtosecond lase system. BS (beam sample), AP (apetue), L (ND ilte), WP (polaization wave plate), VND (vaiable ND ilte), DL (optical vaiable delay line with etoelecto.), DM (photodetecto o the monitoing beam), DR (photodetecto o the eeence beam), and DE (photodetecto beam o the pobe beam intensity). Chem. Phys. Lett., 7[,] () - ime / ps ime poile o the tansient absobance o bianthyl in acetonitile, monitoed at 68-nm ollowing the excitation with a emtosecond nm lase pulse with 8 s whm. Solid line is the cuve calculated on the basis o pulse duation o pump and pobe pulses and the time constant o. ps. J. Phys. Chem., A 6 [] () Absobance ime / s Oxazine /methanol A-Dhv (A-D) (A - D + ). Absobance (./div.) 6 ps ps ps ps ps ps ps 6 8 Wavelength/nm, EADMPP.PRM DMA DMPP/Ethyl Acetate(Exc. at nm) ig. E(a) Absobance t=7 ps. ime / ps DMA DMPP/ethyl acetate (Mon. nm, Exc. nm) Dono Chem. Phys. Lett., 7[] (999)- A - D Accepte 8

9 Chem. Phys. Lett. 78(99). (p.) + BP + DABCO BP - + DABCO + BP BP + BH BPK BOH / BOH P BP d BH + + Q BP 7 6 () () / [BH] / - M q BPK BOH Φ Φ Φ d [ Q] Φ BOH BOH isc Φ Φ Φ BOH d p BOH BOH d [ BH ] [ BH ] [ Q] [ BH ] Φ [ BH ] ( [ BH ]) Φ [ BH ] Φ [ BH ] Φ isc p q [Q] isc Φ ( [ BH ] q[ Q]) Φ [ BH ] q[ Q] Φ Φ [ BH ] / 6 / 7 Φ Φ BOH BOH Φ d [ BH ] Φ [ BH ] [ Q] [ BH ] Φ [ BH ] [ Q] BOH d p d isc p q q / BOH [Q] / M Q 9

10 (Sten-Volme Plot) da I A d A dt I A A d I A I A I / I [Q] / M Kinetic Scheme d I [ Q] d q I d q [ Q] q[ Q] ΦR d q[ Q] d q[ Q] Φ [ Q] [ Q] R q q 8 (89nm) 9 Δλ-nm % ND

11 8. 8. P. BK7 >nm >nm >nm p.6 (p.) - - (S ) ( ) ( ) (S ) di = /M/s / ( di [O ]) = -8 = ns ns - ns

12 8. p. 6 7 (a). Absobance.... Wavelength / nm h N lase = YAG nm (mj/pulse) Hz H + t t dcr I t dt l R CR l t t ln ln ln R I ODα (P)(R) dcr dt t t t C R C P R P I ( t) l ( t) t t l l t t t Saotome et al. Photochem. Photobiol. Sci., [] () (a). Absobance. (b). Absobance. = % % % N lase = % % % N lase ig.(a) (b). Absobance.. = 7% % N lase Saotome et al. Photochemical & Photobiological Sciences,, 8 9

13 Summay Kinetics,Mechanism A + Q AQ Dynamics (ime-window CSPC module PC Lase X-Y stage D PD sample objective counts ime/s time : (D+D) oute delay D APD EOM APD D BBO Bee 8nm,8MHz pin hole μm 9ps counts Events ime/ns D : (D+D) Delay/ns D : D

14 Scan speed. μm/s nm Scan speed. μm/s deocus nm Re. J. Endelein et al J.Opt.Soc.Am.B,,,-9 Polyme,6,7,-8 6

15 Deocusing CW (88nm) CCD Cascade B ~ 9 K PMMA g=78k ms~s ame ~ 9 K PMA g=8k sec. sec. 6sec. 9sec. PMA =8K) sec. sec. PMMA=78K)

16 luoescence Imaging with One Nanomete Accuacy (IONA) A. Yildiz, and P. R. Selvin, Acc. Chem. Res. 8, 7-8 (). X = 7. +/- 9 pixel Y = 8.7 +/- pixel. nm /pixel 8//8 at 6 Single Molecule acing (SM) o a PDI molecule in the uneacted ilm Dt < > nm

17 Cw ns Events Events 68 - Delay /ns - Delay /ns B A A B 7 7 7

2004/11/17 「光化学の基礎概念と実験技術６」

2004/11/17 「光化学の基礎概念と実験技術６」 25//7 http://www.laser.chem.es.osaa-u.ac.jp/ miyasaa@chem.es.osaa-u.ac.jp 2 C-H (4. ev) 29 nm fs psps nsns Internal conversion Intersystem crossing s s f r f f i isc 4 5 Donor Accepter A - D 6 Point-dipole